Sound velocity measurement in liquid water up to 25 GPa and 900 K: Implications for densities of water at lower mantle conditions

We extended the pressure range of sound velocity measurements for liquid water to 25 GPa and 900 K along the melting curve using a laser heated diamond anvil cell with a combined system of Brillouin scattering and synchrotron X-ray diffraction. Experimental pressure and temperature were obtained by solving simultaneous equations: the melting curve of ice and the equation of state for gold. The sound velocities obtained in liquid water at high pressures and melting temperatures were converted to density using Murnaghan's equation of state by fitting a parameter of the pressure derivative of bulk modulus at 1 GPa. The results are in good agreement with the values predicted by a previously reported equation of state for water based on sound velocity measurements. The equation of state for water obtained in this study could be applicable to water released by dehydration reactions of dense hydrous magnesium silicate phases in cold subducting slabs at lower mantle conditions, although the validity of Murnaghan's equation of state for water should be evaluated in a wider pressure and temperature ranges. The present velocity data provides the basis for future improvement of the accurate thermodynamic model for water at high pressures.     

The relation between Cu/Au ratio and formation depth of porphyry-style Cu–Au ± Mo deposits

Constraints on gold and copper ore grades in porphyry-style Cu–Au ± Mo deposits are re-examined, with particular emphasis on published fluid pressure and formation depth as indicated by fluid inclusion data and geological reconstruction. Defining an arbitrary subdivision at a molar Cu/Au ratio of 4.0 × 10⁴, copper–gold deposits have a shallower average depth of formation (2.1 km) compared with the average depth of copper–molybdenum deposits (3.7 km), based on assumed lithostatic fluid pressure from microthermometry. The correlation of Cu/Au ratio with depth is primarily influenced by the variations of total Au grade. Despite local mineralogical controls within some ore deposits, the overall Cu/Au ratio of the deposits does not show a significant correlation with the predominant type of Cu–Fe sulfide, i.e., chalcopyrite or bornite. Primary magma source probably contributes to metal endowment on the province scale and in some individual deposits, but does not explain the broad correlation of metal ratios with the pressure of ore formation. By comparison with published experimental and fluid analytical data, the observed correlation of the Cu/Au ratio with fluid pressure can be explained by dominant transport of Cu and Au in a buoyant S-rich vapor, coexisting with minor brine in two-phase magmatic hydrothermal systems. At relatively shallow depth (approximately <3 km), the solubility of both metals decreases rapidly with decreasing density of the ascending vapor plume, forcing both Cu and Au to be coprecipitated. In contrast, magmatic vapor cooling at deeper levels (approximately >3 km) and greater confining pressure is likely to precipitate copper ± molybdenum only, while sulfur-complexed gold remains dissolved in the relatively dense vapor. Upon cooling, this vapor may ultimately contract to a low-salinity epithermal liquid, which can contribute to the formation of epithermal gold deposits several kilometers above the Au-poor porphyry Cu–(Mo) deposit. These findings and interpretations imply that petrographic inspection of fluid inclusion density may be used as an exploration indicator. Low-pressure brine + vapor systems are favorable for coprecipitation of both metals, leading to Au-rich porphyry–copper–gold deposits. Epithermal gold deposits may be associated with such shallow systems, but are likely to derive their ore-forming components from a deeper source, which may include a deeply hidden porphyry–copper ± molybdenum deposit. Exposed high-pressure brine + vapor systems, or stockwork veins containing a single type of intermediate-density inclusions, are more likely to be prospective for porphyry–copper ± molybdenum deposits.     

Iron oxidation state of a 2.45-Byr-old paleosol developed on mafic volcanics

The 2.45-Byr-old weathering profile developed on early Proterozoic mafic volcanics located near Cooper Lake, Ontario, Canada, was examined geochemically and mineralogically for a better understanding of the atmospheric oxygen evolution. Ferrous to ferric ion, Fe(II) and Fe(III), respectively, ratios of the bulk rock samples were analyzed by Mössbauer spectrometry. The total Fe (Fe(T)) and Fe(II) concentrations decrease from 12.0 and 11.2 wt.% to 1.85 and 0.89 wt.%, respectively, from the bottom to the top of the weathering profile. The Fe(T) and Fe(II) concentrations normalized to Ti and Zr, as well as the Fe(II)/Fe(III) ratio of raw data, linearly decrease with depth toward the top, while the Fe(III) concentration remains nearly constant throughout the profile. The linear decrease of Fe(II), accompanied by the nearly constant distribution of Fe(III), is difficult to be explained by the scenario of oxidizing weathering and subsequent reducing hydrothermal alteration. The behaviors of Fe(II) and Fe(III) can be simply explained by anoxic weathering. The anoxic weathering suggests that the 2.45-Ga atmosphere was anoxic. The slight increase of Fe/(Fe+Mg) in the octahedral sites of chlorite toward the top and no Ce anomaly in the REE patterns are also consistent with anoxic weathering.     

The development of Fe-nodules surrounding biological material mediated by microorganisms

Takashikozo is a phenomenon of Quaternary sediments in Japan. They are cylindrical Fe-oxyhydroxide nodules that form as plaques round plant roots, where Fe is preferentially concentrated to develop a solid wall. Structural features suggest that after the roots have decayed, the central space where the roots were situated acts as a flow path for oxidized water. Analysis of microbial 16S rDNA extracted from the nodules identified iron-oxidizing bacteria encrusted round the roots where they are the likely initiators of nodule formation. Direct microscopic observation revealed an accumulation of Fe-oxyhydroxides that fill the pore spaces and is also likely to be linked with the encrusting microbial colonies. Geological history and nanofossil evidence suggest that these Fe-nodules may have been buried at a depth of up to several tens of meters for at least 10⁵ years in reducing Quaternary sediments. Thus Fe-oxyhydroxide nodules that have formed in a geological environment at the interfaces between water and rock by microbial mediation can persist under reducing conditions. If this is the case, the phenomenon is significant as an analogue of post-closure conditions in radioactive waste repositories, since it could influence nuclide migration.     

Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back-Arc Basin

The Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg^?1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO₂ droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.     

Effects of heavy oil in the developing spotted halibut, Verasper variegatus

It is well known that heavy oil (HO) on the sea surface causes serious problems in the aquatic environment. In particular, some species of teleosts which develop on the sea surface are thought to be affected by the HO which flows out from tankers or coastal industry. However, the toxicological effects of HO are not fully understood. We performed exposure experiments using the Pleuronectiformean fish, spotted halibut (Verasper variegatus), which is an important fishery resource in Japan. In course of the development, HO-exposed embryos showed remarkable delay in developmental processes including somite formation. We further observed abnormal development of the head morphology. Notably, treated embryos had relatively small eyes and craniofacial structures. These findings strongly suggest that HO seriously affects the cell proliferation and differentiation of the embryo. In addition, HO-exposed embryos showed abnormal neuronal development. We also performed the exposure in the larval stage. Treatment of post-hatching larvae with HO resulted in significantly greater mortality compared with controls. Through these observations, we finally conclude that HO is strongly toxic to halibut in their early life stages.     

Gas hydrate saturation at Site C0002, IODP Expeditions 314 and 315, in the Kumano Basin,Nankai trough

The degree of gas hydrate saturation at Integrated Ocean Drilling Program (IODP) Site C0002 in the Kumano Basin, Nankai Trough, was estimated from logging‐while‐drilling logs and core samples obtained during IODP Expeditions 314 and 315. Sediment porosity data necessary for the calculation of saturation were obtained from both core samples and density logs. Two forms of the Archie equation (‘quick‐look’ and ‘standard’) were used to calculate gas hydrate saturation from two types of electrical resistivity log data (ring resistivity and bit resistivity), and a three‐phase Biot‐type equation was used to calculate gas hydrate saturation from P‐wave velocity log data. The gas hydrate saturation baseline calculated from both resistivity logs ranges from 0% to 35%, and that calculated from the P‐wave velocity log ranges from 0% to 30%. High levels of gas hydrate saturation (>60%) are present as spikes in the ring resistivity log and correspond to the presence of gas hydrate concentrations within sandy layers. At several depths, saturation values obtained from P‐wave velocity data are lower than those obtained from bit resistivity data; this discrepancy is related to the presence of free gas at these depths. Previous research has suggested that gas from deep levels in the Kumano Basin has migrated up‐dip towards the southern and seaward edge of the basin near Site C0002. The high saturation values and presence of free gas at site C0002 suggest that a large gas flux is flowing to the southern and seaward edge of the basin from a deeper and/or more landward part of the Kumano Basin, with the southern edge of the Kumano Basin (the location of site C0002) being the main area of fluid accumulation.     

Preferred orientation of the trace fossil Entradichnus meniscus in eolian dune strata (Djadokhta Formation) at Tugrikiin Shiree,southern Mongolia and its paleoecological implications

Eolian sand dune deposits of the Upper Cretaceous Djadokhta Formation at Tugrikiin Shiree, southern Mongolia, yield not only dinosaur skeletal remains but also numerous trace fossils produced by invertebrates. This paper describes the trace fossil Entradichnus meniscus, a long unlined and unbranched trail that is filled with meniscate laminae and occurs characteristically in positive epirelief. The trail is straight to gently meandering, parallel to the foreset laminae of the eolian dunes, and exhibits a significant preferred orientation parallel to the depositional dip of the cross‐stratification laminae. In addition, almost all the crescentic internal laminae of the trail show concave down‐dips. These features indicate that the trails were produced beneath the slipface of eolian dunes by the downward burrowing of the trace‐makers. This occurrence mode of E. meniscus of the Mongolian Cretaceous is very similar to that described from the Jurassic eolian dune deposits in North America. Hence, the downward burrowing of the E. meniscus animal might be a common feature in arid eolian dune deposits at least during the Jurassic and Cretaceous, and possibly reflecting a behavioral response to the morphology of large sand dunes under an arid climate.     

Frequency–Magnitude Distribution of −3.7 ≤ M W ≤ 1 Mining-Induced Earthquakes Around a Mining Front and b Value Invariance with Post-Blast Time

We investigated frequency-magnitude distribution (FMD) of acoustic emissions (AE) occurring near an active mining front in a South African gold mine, using a catalog developed from an AE network, which is capable of detecting AEs down to M _W  ?5. When records of blasts were removed, FMDs of AEs obeyed a Gutenberg?Richter law with similar b values, not depending on post-blasting time from the initial 1-min interval through more than 30 h. This result denies a suggestion in a previous study (Richardson and Jordan Bull Seismol Soc Am, 92:1766–1782, 2002) that new fractures generated by blasting disturb the size distribution of background events, which they interpreted as slip events on existing weak planes. Our AE catalog showed that the GR law with b ～ 1.2 was valid between M _W  ?3.7 and 0 for AEs around the mining front. Further, using the mine’s seismic catalog, which covers a longer time period of the same area, we could extend the validity range of the GR law with the same b value up to M _W 1.     

Toxicogenomic analysis of immune system-related genes in Japanese flounder (Paralichthys olivaceus) exposed to heavy oil

Heavy oil contamination is one of the most important environmental issues. Toxicities of polycyclic aromatic hydrocarbons (PAHs), including immune toxicities, are well characterized, however, the immune toxic effects of heavy oil, as a complex mixture of PAHs, have not been investigated. In the present study, we selected Japanese flounder (Paralichthys olivaceus) as a model organism, and observed alteration of immune function by the exposure to heavy oil. To analyze the expression profiles of immune system-related genes, we selected 309 cDNAs from our flounder EST library, and spotted them on a glass slide. Using this cDNA array, alteration of gene expression profiles was analyzed in the kidneys of flounders exposed to heavy oil. Six Japanese flounders (mean body weight: 197 g) were acclimated to laboratory conditions at 19-20 degrees C. Three fish were exposed to heavy oil C (bunker C) at a concentration of 3.8 g/L for 3 days, and the others were kept in seawater without heavy oil and used as the control. After the exposure period, the fish were transferred into control seawater and maintained for 4 days, and then they were dissected and their kidneys were removed. Total RNA was extracted from the kidney samples to use in gene expression analyses. The microarray detected alteration of immune system-related genes in the kidneys of heavy oil-exposed flounders, including down-regulation of immunoglobulin light chain, CD45, major histocompatibility complex class II antigens and macrophage colony-stimulating factor precursor, and up-regulation of interleukin-8 and lysozyme. These results suggest that pathogen resistance may be weakened in heavy oil-exposed fish, causing a subsequent bacterial infection, and then proinflammatory genes may be induced as a defensive response against the infection. Additionally, we found candidate genes for use as biomarkers of heavy oil exposure, such as N-myc downstream regulated gene 1 and heat shock cognate 71 kDa proteins.